Process for preparing alternating copolymer of butadiene and alphaolefine and novel alternating copolymer of butadiene and alphaolefine containing cis configuration butadiene unit

ABSTRACT

A PROCESS FOR PREPARING ALTERNATING COPOLYMER OF BUTADIENE AND A-OLEFINE WHICH COMPRISES CONTACTING BUTADIENE AND THE A-OLEFINE IN LIQUID PHASE WITH A CATALYST SYSTEM COMPRISING THE FIRST COMPONENET OF A1R3 WHEREIN R REPRESENTS A HYDROCARBON RADICAL SELECTED FROM THE GROUP CONSISTING OF ALKYL, ARYL AND CYCLOALKYL RADICAL IN WHICH AT LEAST ONE R IS SELECTED FROM THE GROUP CONSISTING OF ALKYL HAVING AT LEAST 3 CARBON ATOMS PER ONE MOLECULE, ARYL AND CYCLOALKYL RADICAL AND THE SECOND COMPONENET OF TIX&#39;&#39;4 WHEREIN X&#39;&#39; IS SELECTED FROM THE GROUP CONSISTING OF CHLORINE, BROMINE AND IODINE, OR A CATALYST SYSTEM COMPRISING THE FIRST COMPONENET OF A1R3 WHEREIN R REPRESENTS A HYDROCARBON RADICAL SELECTED FROM THE GROUP CONSISTING OF ALKYL, ARYL AND CYCLOALKYL RADICAL, AND THE SECOND COMPONENET OF TIX&#39;&#39;4 WHEREIN X&#39;&#39; IS THE SAME AS THAT DEFINED ABOVE AND THE THIRD COMPONENET OF A CARBONYL GROUP-CONTAINING COMPOUND. AN ALTERNATING COPOLYMER OF BUTADIENE AND A-OLEFINE, THE MICROSTRUCTURE OF BUTADIENE UNIT OF THE ALTERNATING COPOLYMER CONTAINS CIS-CONFIUGRATION. THE ALTERNATING COPOLYMERS ARE RUBBER-LIKE IN CHARACTER AND CAN BE USED AS POLYMERIC PLASTICIZERS, IN ADHESIVES AND CAN BE VULCANIZED WITH SULFUR OR A SULFUR COMPOUND TO PRODUCE VULCANIZED ELASTOMERS.

Oct. 16, 1973 u-u o w s ET AL 3,766,153

PROCESS FOR PREPARING ALTERNATING COPOLYMER OF BUTADIENE AND ALPHA-OLEFlNE AND NOVEL ALTERNATING COPOLYMER OF BUTADIENE AND ALPHAOLEFINE CONTAINING CIS'CONFIGURATION BUTADIENE UNIT Original Filed May 8, 1970 5 Sheets-Sheet 3500' 2500' I900 1700' 1500' 1300' I100 900' 700 3000 2000 I800 I600 I400 I200 I000 800 Oct. 16, 1973 AKlHlRo KAWASAKI ET AL 3,766,153

PROCESS FOR PREPARING ALTERNATING COPOLYMER 0F BUTADIENE AND ALPHA-OLEFINE AND NOVEL ALTERNATING COPOLYMER OF BUTADIENE AND ALPHA-OLEFINE CONTAINING SIS-CONFIGURATION BUTADIENE UNIT Griginal Filed May 8, 1970 5 Sheets-Sheet 2 3500' 2500 1900 1700 1500' I300 n00 900' 700 3000 2000 I800 I600 I400 1200 000 800 Oct. 16, 1973 AK|H|RO w s Kl ETAL 3,766,153

PROCESS FOR PREPARING ALTERNATING COPOLYMER OF BUTADIENE AND ALPHA-OLEFlNE AND NOVEL ALTERNATING COPOLYMER OF BUTADIENE AND ALPHA-OLEFINE CONTAINING CIS-CONFIGURATION BUTADIENE UNIT Original Filed May 8, 1970 5 Sheets-Sheet 5 5500' 2500 I900 I700 I500 I300 II00' 900' 700 5000 2000 I800 I600 I400 I200 I000 800 Oct. 16, 1973 AKIHIRO K WAS KI ET AL 3,766,153

' PROCESS FOR PREPARING ALTERNATING COPOLYMER OF BUTADIENE AND ALPHA-OLEFlNE AND NOVEL ALTERNATING COPOLYMER OF BUTADIENE AND ALPHA-OLEFINE CONTAINING CIS-CONFIGURATION BUTADIENE UNIT Griginal Filed May 8, 1970 5 Sheets-Sheet 4 5500' 2500 1900' I700 I500 I300 H00 900 760 30002000000 I600 |400 |200|000800 Oct. 16, 1973 AKIHIRQ KI ETAL 3,766,153

PROCESS FOR PREPARING ALTERNATING COPOLYMER OF BUTADIENE AND ALPHA-OLEFlNE AND NOVEL ALTERNATING COPOLYMER OF BUTADIENE AND ALPHA-OLEFINE CONTAINING CIS-CONFIGURATION BUTADIENE UNIT Original Filed May 8, 1970 5 Sheets-Sheet 5 3 2500 1900 I700 I500 I500 H00 900' 700 29000 2000 I800 I600 I400 1200 I000 800 United States Patent O US. Cl. 260-841 9 Claims ABSTRACT OF THE DISCLOSURE A process for preparing alternating copolymer of butadiene and a-olefine which comprises contacting butadiene and the a-olefine in liquid phase with a catalyst system comprising the first component of AIR, wherein R represents a hydrocarbon radical selected from the group consisting of alkyl, aryl and cycloalkyl radical in which at least one R is selected from the group consisting of alkyl having at least 3 carbon atoms per one molecule, aryl and cycloalkyl radical and the second component of TiX', wherein X is selected from the group consisting of chlo rine, bromine and iodine, or a catalyst system comprising the first component of AIR, wherein R represents a hydrocarbon radical selected from the group consisting of alkyl, aryl and cycloalkyl radical, and the second component of TiX' wherein X' is the same as that defined above and the third component of a carbonyl group-containing compound. An alternating copolymer of butadiene and a-olefine, the microstructure of butadiene unit of the alternating copolymer contains cis-configuration. The alternating copolymers are rubber-like in character and can be used as polymeric plasticizers, in adhesives and can be vulcanized with sulfur or a sulfur compound to produce vulcanized elastomers.

RELATED APPLICATIONS This application is related to applications Ser. Nos. 884,- 479 and 884,871, filed Dec. 12 and 15, 1969, respectively, and now Pat. Nos. 3,652,519 and 3,652,518, each of Mar. 28, 1972.

This is a division of application Ser. No. 35,637, filed May 8, 1970, now US. 3,714,133.

BACKGROUND OF THE INVENTION (1) Field of the invention The present invention relates to a process for preparing an alternating copolymer of butadiene and u-olefine and a novel alternating copolymer obtained thereby. The novel alternating copolymer of this invention contains considerable amounts of cis-configuration butadiene unit.

(2) Description of the prior art Because of its chipping and cutting properties and its low skid resistance, the demand for cis-1.4 polybutadiene in the field of automobile tires is not so large as was expected at first. The defects have been ascribed to its unbranched straight-chain structure. In order to overcome these defects, many attempts have been made to produce alternating copolymers of butadiene and Ot-OlGfiIJB, for example, butadiene and propylene, butadiene and l-butene, etc. However, in general, it is not easy to produce even a random copolymer of butadiene and a-olefine by an ionic catalyst.

For instance, German Pat. 1,173,254 claims a process ice for preparing a copolymer of conjugated diene and monoolefine using vanadium (V) oxychloride as the catalyst, but the examples do not show a copolymerization reaction of butadiene and propylene. German Pat. 1,144,924 claims a process for preparing a copolymer of diene and ethylene or propylene by using a catalyst system consisting of a compound of Ti, Zr, Ce, V, Nb, Ta, Cr, M0 or W in which the metal is at least in part below a valency of 3. This patent shows the copolymerization reaction of. butadiene and ethylene by titanium tetrachloride-lithiumaluminum hydride, titanium tetrachloride-phenylmagne' sium bromide, titanium tetrachloride-sodium dispersion, zirconium tetrachloride-tintetrabutyl and tetraoctyltitanate-phenylmagnesium bromide catalyst systems in its examples, but a process for preparing a copolymer of butadiene and propylene is not shown. Belgian Pat. 625,657 also describes a process for preparing coand terpolymers of butadiene with ethylene and (or) a-olefines by using a catalyst system containing a hydrocarbon-soluble vanadium compound and an organoaluminum compound containing more than one organic group having strong sterical hindrance, e.g. 3-methyl-butyl, cycloalkyl or cyclopenthyl methyl, and it claims a process for preparing ethylene-propylenebutadiene terpolymer. However, no example of butadiene-propylene copolymer is shown in it.

On the other hand, British Pat. 1,108,630 shows a process for preparing a rubbery random copolymer of butadiene and propylene of high molecular weight with high content of propylene by using a three components catalyst system consisting of trialkylaluminum, iodine and a compound having the general formula of TiBr Cl wherein n is zero or an integer of 1 to 4. The microstructure of butadiene unit and the content of propylene unit in the copolymer are shown in the patent. But there are shown no experimental results which support the assumption which the copolymer should be a random copolymer of butadiene and propylene. A random copolymer of butadiene and propylene was also prepared by using a catalyst system consisting of triethylaluminum, titanium tetrachloride and polypropylene oxide. Polypropylene oxide was used as a randomizer and therefore a copolymer of butadiene and propylene prepared by the catalyst system of triethylaluminum and titanium tetrachloride was shown to be blocktype. The molar ratio of triethylaluminum to titanium tetrachloride was 1.08 (Al/Ti=1.08) (paper presented at 2nd Symposium on Polymer Synthesis, Tokyo, Oct. 5, 1968, the Society of Polymer Science, Japan). British Pat. 1,026,615 claims a process for preparing a random copolymer of butadiene and propylene by forming a catalyst system of triethylaluminum and titanium tetrachloride in the presence of propylene, and then adding butadiene to the catalyst system. According to the patent, the propylene content of the copolymer was much higher than that of the copolymer prepared by the catalyst formed after the monomers were mixed. This result is inconsistent with the result described in the above paper. A copolymerization reaction of butadiene and pro pylene was also carried out by using a catalyst system of triethylaluminum and titanium tetrachloride prepared in propylene and the product was confirmed, by fractional precipitation test, to be a copolymer of butadiene and propylene (Chemistry of High Polymers, The Society of Polymer Science, Japan, 20, 461 (1963)). The molar ratio of triethylaluminum to titanium tetrachloride of the above catalyst system was 1.5 (Al/Ti=1.5). The content of this paper corresponds to that of the above British patent, but there is no description in it showing that the copolymer should be a random copolymer of butadiene and propylene.

According to the methods of British Patent 982,708, a mixture containing -95 mole percent butadiene, the

rest being 4-methyl-l-pentene, is polymerized at a temperature in the range to 30 C. by a catalyst system which is the reaction product of vanadium (V) oxychloride with triisobutylaluminum, an aluminum-dialkyl monochloride or an aluminum sesquialkyl chloride. The microstructure of the copolymer is not shown in the patent. British Patent 924,654 describes a process for preparing a copolymer of butadiene and propylene by using an Alfin" catalyst. The copolymer showed a characteristic infra-red absorption band at 11.95 microns. It was ascribed to trisubstituted ethylene structure. Therefore, the result does not support the assumption that the copolymer should be a random or alternating copolymer of butadiene and propylene.

Recently, Furukawa et al. also reported the process of preparing alternating copolymers of butadiene and a-olefine by using vanadyl (V) chloride-diethylaluminum monochloride-triethylaluminum catalyst system (22nd Annual Meeting of Japan Chemical Society, Tokyo, Mar. 31, 1969). However, the molecular weight of the copolymer was very low and its intrinsic viscosity did not exceed 0.1 dl./g.

Consequently, as far as the inventors know, with the exception of the methods of Furukawa et al. described above, there is no prior art in connection with alternating copolymers of butadiene and u-olefine nor of a process for their preparation.

SUMMARY OF THE INVENTION The object of the present invention is to provide new catalytic systems giving high molecular weight alternating copolymer of butadiene and a-olefine in high yield.

In accordance with this invention, we have found that by using the catalyst system composed of the first component of an organoaluminum compound having the general formula of AlR wherein R represents a hydrocarbon radical selected from the group consisting of alkyl, aryl and cycloalkyl radicals and at least one R is selected from the group consisting of an alkyl radical having at least 3 carbon atoms, aryl radical and cycloalkyl radical and the second component of titanium tetrahalide having the general formula of TiX' (wherein X represents chlorine, bromine or iodine, hereinafter the same) or by using the catalyst system composed of the first component of AlR wherein R represents a hydrocarbon radical selected from the group consisting of alkyl, aryl and cycloalkyl radicals, the second component of TiX' (wherein X is the same as that defined above) and the third component of a carbonyl group-containing compound, high molecular weight alternating copolymers of butadiene and a-olefine can be produced in high yield. We have also found that by adding halogen (fluorine inclusive), halogen (fluorine inclusive) containing compound, metal oxide or metalloid oxide to the above mentioned catalyst systems, the catalytic properties of the above mentioned catalysts can be further improved.

The alternating copolymers of this invention are rubberlike in character and can be used as polymeric plasticizers, 1n adhesives and can be vulcanized with sulfur or a sulfur compound to produce vulcanized elastomers.

The microstructure of butadiene unit of the alternating copolymer of butadiene and a-olefine prepared by the methods of Furukawa et al. described above was trans 1.4-configuration. The main components forming the catalyst systems were an organoaluminum compound and a vanadium compound. On the other hand the main components forming the catalyst systems of this invention are an organoaluminum compound and a titanium compound and moreover considerable amounts of cis 1.4-configuration and small amounts of 1.2-configuration are found in the butadiene unit of the alternating copolymer. In other words the structure of the alternating copolymer prepared by the catalyst system of an organoaluminum compound and a vanadium compound previously reported is different from that of the a ter a copolymer P pared by the catalyst system of an organoaluminum compound and a titanium compound of this invention. Therefore the alternating copolymers of butadiene and u-olefine prepared by the process of this invention are new materials.

The carbonyl group containing compound which form the third component of the catalyst systems of this invention are carbon dioxide, aldehyde, keto-aldehyde, ketone, carboxylic acid, keto-carboxylic acid, oxy-carboxylic acid, carboxylic acid halide, keto-carboxylic acid halide, oxy-carboxylic acid halide, carboxylic acid anhydride, keto-carboxylic acid anhydride, oxy-carboxylic acid anhydride, salt of carboxylic acid, salt of keto-carboxylic acid, salt of oxy-carboxylic acid, ester of carboxylic acid, ester of keto-carboxylic acid, ester of oxy-carboxylic acid, carbonyl halide, carbonate, carbonic ester, lactone, ketene, quinone, acyl peroxide, metal complex involving carbonyl group, acid amide, acid irnide, isocyanate, aminoacid, urein, ureide, salt of carbamic acid, ester of carbamic acid, ureide acid, etc.

The halogen used as the other third component of the catalyst system of this invention is chlorine, bromine iodine or fluorine. The halogen compounds which form the other third component of the catalyst system of this invention are the compounds having transition metal-X linkage (X is halogen) such as compounds having the general formulae VX4, VOX3, WXG, MOX5, CrO X ZI'X4, FeX OV(OR),,X (R is a hydrocarbon radical such as alkyl radical, aryl radical or cycloalkyl radical, hereinafter the same, and n is a number from 1 to 2), Zr(OR) X Ti(OR) X (n is a number from 1 to 3), Zr(OR) X, OV(C H O ),,X (n is a number from 1 to 2), V(C I-I ),,X (n is a number from 1 to 2, V(C H X, 5 5) 2 5 5)2 5 5) 3 5 5)2 2 5 5) z s zJz 5 5) )3 (C H -IrX etc.; and alkane compounds having C-X linkage wherein X is halogen such as tert-butyl chloride, tert-butyl bromide, tert-butyl iodide, sec-butyl chloride, sec-butyl bromide, sec-butyl iodide, carbon tetrachloride, carbon tetrabromide, carbon tetraiodide, etc.; Lewis acidbase complex compounds which formed from halogen compounds showing Lewis acid property such as compounds of the general formulae H X (wherein X is halogen, hereinafter the same), CuX, ZnX BiX FeX SnX BX AlX AlR,,X (R is a hydrocarbon radical such as alkyl radical, aryl radical or cycloalkyl radical, hereinafter the same, and n is a number from 1 to 2), VOX VX4, CI'OZXZ, NlXg, MOX5, ZIX4, PX5, SbX5, WX MnX M X and the like. Lewis base such as ether, pyridine, amine, phosphine, derivatives of these compounds, etc., are also employed. The halogen compounds which form the fourth component of the catalyst system of this invention are the ones showing Lewis acid property such as compounds of the general formulae VX, (wherein X is halogen, hereinafter the same), VOX WX MOX5, CIOzXg, ZI'X4, FGX3, BX3, PX5, SHX4, SbX5, AlOX, AlX AlR,,X;, (R is a hydrocarbon radical such as alkyl radical, aryl radical or cycloalkyl radical and n is a number from 1 to 2), WX CuX, MnX MgX ZnX HgX BiX NiX etc.; Lewis base complex compounds of the above mentioned h'alogen compounds showing Lewis acid property such as compounds of the general formulae A1X3-O(C2H5)2, BX3-0(C2H5)2, Zl'lXz-PY (wherein Py represents pyridine, hereinafter the same), VOCl 2 5)2 a' y, Fe 2 5)2 8 2" y, -i organoaluminum compounds having Al-X linkage such as compounds of Al(OR) X (n is a number from 1 to 2), etc., organotransition metal compounds having transition metal-X linkage such as compounds of the general formulae OV(OR),,X (n is a number from 1 to 2), Ti(OR),,X (n is a number from 1 to 3), Zr(OR) X Zr(OR) X, OV(C H O X (n is a number from 1 t0 2), V(C H X (n is a number from 1 to 2), 5 5)2 5 5) 2 5 5)2 5 5) 3 Ti(C H X (C H )Ti(OR)X (C H CrX, (C H Mo(CO) X, (C H IrX etc.; halogenated alkane comcounds such as tert-butyl halide, sec-butyl halide, carbon tetrahalide, etc. The metal oxide or metalloid oxide which forms the other fourth component of the catalyst system of the present invention are magnesium oxide, zinc oxide,

6 copolymer of butadiene and pentene-l prepared by the process of this invention;

FIG. 6 shows the nuclear magnetic resonance spectrum of the copolymer;

FIG. 7 shows the infra-red spectrum of the methyl aluminum oxide, titanium dioxide, vanadium pentoxide, 5 ethyl ketone insoluble and diethyl ether soluble alternatsilicon dioxide, silica-alumina, zeolite, boron trioxide, etc. ing copolymer of butadiene and butene-l prepared by the In the preferred embodiment, the molar ratio of organoprocess of this invention; aluminum compound which forms the first component FIG. 8 shows the nuclear magnetic resonance specof the catalyst system of the present invention to titanium trum of the copolymer; tetrahalide which forms the second component of the FIG. 9 shows the infra-red spectrum of the alternating catalyst system should be higher than 1.5 Al/Ti 1.5). copolymer of butadiene and styrene prepared by the The olefine should be one having the general formula: process of this invention; and

FIG. 10 shows the nuclear magnetic resonance CH2 CHR spectrum of the copolymer. (in this formula, K may be a normal chain or branched chain lower alkyl group or a phenyl group). DESCRIPTION OF THE PREFERRED The preparation of the alternating copolymer of buta- EMBODIMENTS di.ene and i i carried.ut by contacting butadiene The invention will be illustrated with reference to the with a-olefine 1n hquid phase in the presence of the catalyst following examples system described above. The copolymerization reaction Example 1 is generally carried out in the presence of a liquid organic diluent. A suitable diluent that can be used for the co- The usual, dry, air-free technique was employed and polymerization reaction is a hydrocarbon compound, such 6.5 milliliters toluene, 0.50 millimole carbonyl group as heptane, octane, isooctane, benzene or toluene. The containing compound and 0.2 milliliter titanium tetratemperature of the copolymerization reaction may be chloride solution in toluene (1 molar solution) were put varied from -l00 C. to 50 C. and sufiicient pressure successively in a 25 milliliters glass bottle at 25 C. Then is employed to keep the monomers in liquid phase. The the bottle was left alone at 25 C. for 10 minutes. Theremolar ratio of butadiene to -olefine in the initial after the bottle was held in a 10W temperautre bath at ono r o iti may b f 2();80 to 8030 d 78 C. and 2.0 milliliters triisobutylaluminum solution more f bl i 5() ;5() in toluene (1 molar solution) and a mixture of 2 milli- At the completion of the copolymerization reaction, liter? fl P p 2 milliliters iq butadiene and h product i i i d d deashed by using a math. 2 milliliters toluene were put successlvely into the bottle anol-hydrochloric acid mixture. The precipitated product also empleylng the usual, y, elf-free techmquee is washed with methanol for several times and dried under after the bottle was Sealed and allowed to p yf t vacuum. Thereafter the product is extracted with methyl at for 15 hours T results are $11I nII1a1'1Zed 1I1 ethyl ketone and diethyl ether successively. The methyl Table AS be seen Table 1, the Yleld of hlgh ethyl ketone soluble fraction is a low molecular weight meleeular Welght alternatlng copolymer Increased y alternating copolymer and methyl ethyl ketone insoluble uslng three eemponents catalyst y and diethyl ether soluble fraction is a high molecular The fellewlng results e pp the e011e111S10I1 that the weight alternating copolymer. copolymer is an alternating copolymer of butadiene and propy ene. BRIEF DESCRIPTION OF THE DRAWINGS (l) The composition of the copolymer according to FIG 1 shows h infra-red Spectrum f th methyl the NMR analysis substantially agrees with the calculated ethyl ketone insoluble and diethyl ether soluble alternating Value for the 1:1 copolymer of butadiene and propylene. copolymer of butadiene and propylene prepared by the Copolymer compositions were determined by measuring process of this invention; the ratio of peak area at 4.651- of butadiene unit to that FIG. 2 shows the nuclear magnetic resonance spectrum of doublet at 9.117- and 9.207 of propylene unit. of the copolymer; (2) The copolymerization reaction gives 1:1 copoly- FIG. 3 shows the infra-red spectrum of the methyl ethyl met Over a Wide range of initial monomer composition, ketone insoluble and diethyl ether soluble alternating The p lymerization reaction gives 1:1 copolymer copolymer of butadiene and 4-methyl pentene-l prepared Independently of pelymeflzatlon eby the process of this invention; The 115.5 e band of P py e p y 4 Shows h nuclear magnetic resonance spectrum 1s not shown in its infra-red spectrum. ThlS means at of the copolymer; least that the length of the propylene-propylene repeat- FIG. 5 shows the infra-red spectrum of the methyl ing unit of the copolymer is not so long as to be detected ethyl ketone insoluble and diethyl ether soluble alternating by its infra-red spectrum.

TABLE 1 Alternating copolymer MEK insoluble, diethyl ether soluble fraction Catalysts MEK Microstructure of butadiene Yield unit (percent) l gP iliiiii a i ii Carbonyl compound 01 (g.) (g.) Trans- Cis- 1,2

2.0 0.2 2-chloroethylbenzoat 0.50 0.05 0 2.0 0.2 0. so 0. 23 2.0 0.2 0. 50 0.20 2.0 0.2 0. 50 0. 25 2.0 0.2 Isobutyric acid 0. 50 0.42 2.0 0.2 Benzoic acid 0.50 0.14 2.0 0.2 Monochloroacetic acid- 0. 50 0.17 3.3 g Maleic acid auhydrlde 0. 50 0. 16

Example 2 alternating copolymer of butadiene and propylene was 0.13 g. and that of methyl ethyl ketone insoluble and diethyl ether soluble alternating copolymer of butadiene and propylene was 1.67 g. When the two components catalyst system consisting of 0.5 millimole titanium tetrabromide and 5.0 millimoles triisobutylaluminum was used and the other copolymerization conditions were the same as the example, yield of the methyl ethyl ketone soluble fraction was 0.07 g. and that of methyl ethyl ketone insoluble and diethyl ether soluble fraction was 0.03 g.

The usual, dry, air-free technique was employed and 6.5 milliliters toluene, 0.50 millimole carbonyl group containing compound and 0.2 milliliter titanium tetrachloride solution in toluene (1 molar solution) were put succes- 5 sively in a 25 milliliters glass bottle at 25 C. Then the bottle was left alone at 25 C. for minutes. Thereafter the bottle Was held in a low temperature bath at 78 C. and 2.0 milliliters triisobutylaluminum solution in toluene (1 molar solution) and a mixture of 2 milliliters liquid 10 propylene, 2 milliliters liquid butadiene and 2 milliliters Example 5 toluene were put successively into the bottle also employing the usual, dry, air-free technique. Thereafter the The usual, dry, air-free technique was employed and bottle was sealed and allowed to copolymerize at l5 C. 3.5 milliliters toluene, 0.12 milliliter isobutyric acid and for 16 hours. The results are summarized in Table 2. 0.5 millimole titanium tetraiodide were put successively TABLE 2 Alternating copolymer MEK insoluble, diethyl ether soluble fraction Catalysts MEK Microstructure of butadiene soluble unit (percent) Experiment Aid-Bu); TiCli fraction Yield No. (mmol (mmol) Carbonyl compound lVLmol (g.) (g.) Trans- Cis- 1,2-

2.0 0.2 Diethyl malonate 0. 50 0.35 0.12 74 21 5 2.0 0 2 Ethyl acetate 0. 50 0.30 0.56 60 28 12 2.0 0.2 Acetone 0. 50 0.62 0.42 65 28 7 2. 0 0. 2 Benzaldehyde 0. 50 0 21 0. 18 57 35 8 2.0 0.2 Acetic acid anhydride 0.60 0 17 l 85 64 30 6 Reference"... 2.0 0 2 0.07

Example 3 in a 25 milliliters glass bottle at 25 C. Then the bottle Th usual, y, q Was employed and was left alone at 25 C. for 10 minutes. Thereafter the 6.5 milliliters toluene, varying amounts of carbonyl group bottle was held in a low temperature b h at 7g (3,

contai ing compound and 02 mllllliter tltanPlm tetra and 5.0 milliliters triisobutylaluminum solution in toluene chloride Solu i n i f q molar Solutlon) were (1 molar solution) and a mixture of 2 milliliters liquid p successively in a 25 mllhhtsrs glass bottle at propylene, 2 milliliters liquid butadiene and 2 milliliters Then the bottle was left alone at 25 C. for 10 minutes. toluene, were put successively into the b l also otewasseae an aowe tocoo t-O" toluene (1 molar solution) and a mixture of 2 milliliters f 14 hours Yield of the g g ff l s q f P py 2 milliliters buiadiene and 2 0.10 g. When the two components catalyst system conn ugilit rs ggl ue zg p g 3 32 sisting of 0.5 millimole titanium tetraiodide and 5.0 millias e p 1 g m0 es triisobutylaluminum was used and the other coafter the bottle was Scal d and allowed 10 p m polymerization conditions were the same as the example, ri tgfig C. for 16 hours. The results are summarized in yleld f the alternating copolymer was 0 Catalysts MEK Microstructure of butadiene soluble unit (percent) Experiment AlEta TiClr fraction Yield N0. (mmol) (mmol) Carbonyl compound (g.) (g.) Trans- Cis- 1,2-

1 2.0 0.2 Maleicacidanhydride 0.05 (g.)- 0.11 0.11 57 30 13 2 2.0 0.2 Propionieacid 0.037 (ml-) 0.21 0.21 70 25 6 Reference 2. 0 0. 2 0 0 Example 4 Example 6 The usual, dry, air-free technique was employed and The usual, dry, air-free technique was employed and 3.5 milliliters toluene, 0.12 milliliter acetic acid anhyvarying amounts of carbonyl group containing comdride and 0.5 millimole titanium tetrabromide were put pound, 0.2 milliliter titanium tetrachloride solution in in a 25 milliliters glass bottle at 25 C. Then the bottle toluene (1 molar solution) and 6.5 milliliters toluene was left alone at 25 C. for 10 minutes. Thereafter the Were put successively in a 25 milliliters glass bottle at bottle was held in a low temperature bath at 78 C, 25 C. Then the b01116 was left 310116 at 25 C. for 10 and 5.0 milliliters triisobutylaluminum solution in toluene minutes. Thereafter the bottle was held in a low tem- (1 molar solution) and a mixture of 2 milliliters liquid perature bath at 78 C. and 2.0 milliliters triisobutylpropylene, 2 milliliters liquid butadiene and 2 milliliters aluminum solution in toluene (1 molar solutions) and a toluene were put successively into the bottle also emmixture of 2 milliliters liquid propylene, 2 milliliters ploying the usual, dry, air-free technique. Thereafter the liquid butadiene and 2 milliliters toluene were put sucb tl was l d d ll d to copolymerize t -30 cessively into the bottle also employing the usual dry, air- C. for 14 hours. Yield of the methyl ethyl ketone soluble free technique. Thereafter the bottle was sealed and allowed to copolymerize at 30 C. for 16 hours. The re sults are summarized in Table 4.

TABLE 4 propylene was obtained. Its intrinsic viscosity was 2.26 (dl./g.) in chloroform at 30 C.

Alternating copolymer MEK insoluble, diethyl ether soluble fraction Catalysts MEK Microstructure of butadiene fsolitiible Yield unit; (percent) E t li-B TlCl rat: or 1 Nlgmflmen nm ll (mmol) Carbonyl compound (g.) (g.) Trans- 015- 1,2-

2.0 0.01 0.20 2. 0. 0. 50 1. 30 63 30 7 2.0 0. 0.01 0. 20 75 20 2. 0 0. 0. 05 0. 74 21 5 2.0 0. Aluminum aeetylacetonate. 0.05 0.22 82 15 3 2.0 0. Hexaearbonyl molybdenum 0.05 0.15 83 14 3 2.0 0. 0. 03

The v lcani t'on as r in Example 7 way u za 1 w ca ried out the following The usual, dry, air-free technique was employed and Co 01 mer i gg 6.5 milliliters toluene, varying amounts of carbonyl group if glack 5 containing compound and 0.2 milliliter titanium tetra- Zinc oxid 5 chloride solution in toluene (1 molar solution) were put 5 Sul hu e 2 successively in a milliliters glass bottle at 25 C. Then g 1 the bottle was left alone at 25 C. for 10 minutes. There- Phen 1 1 after the bottle Was held in a low temperature bath at Ben g g -78 C. and 2.0 milliliers triisobutylaluminum solution Z lazy e 1 in toluene (1 molar solution) and a mixture of 2 milliliters liquids propylene, 2 milliters liquid butadiene and 2 milliliters toluene were put successively into the bottle also employing the usual, dry, air-free technique. Thereafter the bottle was sealed and allowed to copolymerize at 30 C. for 16 hours. The results are summarized in Table 5. In the table, 1; means the intrinsic viscosity measured in coloroform at 30 C. FIG. 1 shows the infrared spectrum of the methyl ethyl ketone insoluble and diethyl ether soluble alternating copolymer of were mixed on a roller and vulcanized within 60 minutes at 150 C.

The product obtained by the vulcanization had the following values:

Elongation at break at 25 C.: 330%; Tensile strength at 25 C.: 193 kg./cm. Modulus 300% at 25 C.: 182 kg./cm.

The microstructure of butadiene unit of the copolymer was as follows:

butadiene and propylene prepared by the process of Exp. trans: 68%

No. 3 FIG. 2 shows the nuclear magnetic resonance c1s: 26%

spectrum of the copolymer. 1.2: 6%

TAB LE 5 Alternating copolymer MEK insoluble, diethyl ether soluble fraction Catalysts MEK Mierostrueture of butadiene soluble unit (percent) Experiment Ald-Bu); T1014 fraction Yield [1,

No. (mmol) (mmol) Carbonyl compound Mmol (g.) (g.) (dL/g.) Trans- Cis- 1,2

2. 0 0. 2 0. 19 0. 08 38 7 2.0 0.2 do 0.28 0.21 67 24 9 2. 0 0. 2 .(10 0. 36 0. 79 66 29 5 2. 0 O. 2 d0 0. 13 0. 19 66 28 6 2. 0 0. 2 0. 26 0. 23 72 22 6 2. 0 0. 2 0. 17 0. 44 65 26 9 2. 0 0. 2 0. 03 0. 20 32 8 2. 0 0. 2 0. 16 0. 24 69 25 6 2. 0 0. 2 0. 11 0. 20 50 38 12 2. 0 0. 2 Diphenyl acetic acid 0. 500 0. 21 l. 69 70 24 6 2. 0 0. 2 a-chloropropionio acid- 0. 500 0. l4 0. 94 62 28 10 2. 0 0. 2 Caproic acid 0. 500 0. 52 0. 69 59 33 8 2. 0 0. 2 Phthalic acid anhydride 0. 500 0. 17 0. 44 73 19 8 Example 8 Example 9 The usual, dry, air-free technique was employed and 190 milliliters toluene, 0.8 milliliter propionic acid anhydride and 0.275 milliliter titanium tetrachloride were put successively in a 500 milliliters glass bottle at 25 C. Then the bottle was left alone at 25 C. for 10 minutes. Thereafter the bottle was held in a low temperature bath at -78 C. and 25 milliliters triisobutylaluminum solution in toluene (1 molar solution) and a mixture of 50 milliliters liquid propylene and 50 milliliters liquid butadiene were put successively into the bottle also employing the usual, dry, air-free technique. Thereafter the bottle was sealed and allowed to copolymerize at -30 C. for 42 hours. 58.0 g. alternating copolymer of butadiene and 78 C. and 2.0 milliliters triisobutylaluminum solution in toluene (1 molar solution) and a mixture of 2 milliliters liquid propylene, 2 milliliters liquid butadiene and 2 milliliters toluene were put successively into the bottle 5 also employing the usual, dry, air-free technique. Thereafter the bottle was sealed and allowed to copolymerize at -30 C. for 16 hours. The results are summarized in Table 6.

pound were put successively in a 25 milliliters glass bottle at 25 C. Then the bottle was left alone at 25 C. for 10 TABLE 6 Alternating copolymer MEK insoluble, diethyl ether soluble fraction Catalysts MEK Microstructure of butadiene soluble unit (percent) Experiment Ala-Bu); T101 fraction Yield No. (mmol) (mmol) Carbonyl compound Gram (g.) (g.) Trans- Cis- 1,2-

2.0 0.2 Azodicarbonamide 0.06 0.12 2.0 0.2 Chloracetamide 0.047 0.13 2.0 0. 2 Phenylisocyanate. 0.054 0.19 2.0 0.2 Phenylurethane 0.088 0. 24 2.0 0.2 Benzohydroxamic acld.. 0.07 0.0!) Reference"... 2. 0 0. 2

Milliliter.

Example minutes. Thereafter the bottle was held in a low tempera- The usual, dry, air-free technique was employed and 7.5 milliliters toluene, 0.1 millimole titanium tetrachloride and varying amounts of carbonyl group containing compound were put successively in a milliliters glass bottle at 25 C. Then the bottle was left alone at 25 C. for 10 minutes. Thereafter the bottle was held in a low temperature bath at 78 C. and varying amounts of triisobutylaluminum solution in toluene (1 molar soluture bath and varying amounts of triisobutylaluminum solution in toluene (1 molar solution) and a mixture of 2 milliliters liquid propylene, 2 milliliters liquid butadiene and 2 milliliters toluene were put successively into the bottle also employing the usual, dry, air-free technique. Thereafter the bottle was sealed and allowed to copolymerize at C. for 21 hours. The results are summarized in Table 8.

TABLE 8 Alternating copolymer Catalysts Microstructure of butadiene unit (percent) Experiment Aid-Bu TiBr; Yield No. (mmol) (mmol) Carbonyl compound Mmol (g.) Trans- Cis- 1, 2-

1.0 0.1 Benzalacetophenone 0.25 1.0 0.1 Diketene 0.25 0.5 0.1 p-Methoxybenzoic acid 0.10 0.5 0.1 p-Benzoquinone 0.10 0.5 0 1 Polymethylmethacrylate-. 0.01 Reference 1.-. 1. 0 0.1 Reference 2. 0. 5 0. 1

Gram.

tion) and a mixture of 2 milliliters liquid propylene, 2 Example 12 milliliters liquid butadiene and 2 milliliters toluene were put successively into the bottle also employing the usual,

The usual, dry, air-free technique was employed and dry, air-free technique. Thereafter the bottle was sealed 7.5 milliliters toluene, 0.1 millimole titanium tetrachloride and allowed to copolymerize at -30 C. for 21 hours. The results are summarized in Table 7.

and varying amounts of carbonyl group containing compound were put successively in a 25 milliliters glass bottle TABLE 7 Alternating eopolymer Catalysts Mierostructure of butadiene unit (percent) Experiment Aid-Bu); T1014 Yield No. (mmol) (mmol) Carbonyl compound 01 (g.) Trans- Cis- 1,2-

1.0 0. 1 Terephthalaldehyde 0.25 1. 0 0. 1 Glycolic acid 0.25 0.5 0.1 Carbon dioxide. 0.25 0.5 0.1 Acetophenone-- 0.10 1.0 0.1 Benzil 0.25 1.0 0.1 Polyvinyl acetate.-. 0.01 1.0 0.1 Tartaric acid 0.25 Reference 1-... 1. 0 0.1 Reierence 2... 0. 5 0. 1

l Gram.

Example 11 at 25 C. Then the bottle was left alone at 25 C. for 10 The usual, dry, air-free technique was employed and 7.5 milliliters toluene, 0.1 millimole titanium tetrabromide minutes. Thereafter the bottle was held in a low temperature bath at 78 C. and 1.0 milliliter triisobutylalumiand varying amounts of carbonyl group containing commm solution in toluene (1 molar solution) and a mixture 13 of 2 milliliters liquid propylene, 2 milliliters liquid butadiene and 2 milliliters toluene were put successively into the bottle also employing the usual, dry, air-free technique. Thereafter the bottle was sealed and allowed to copolymerize at 30 C. .for 16 hours. The results are summarized in Table 9.

l4 ride and varying amounts of carbonyl group containing compound were put successively in a 25 milliliters glass bottle at 25 C. Then the bottle was left alone at 25 C. for 10 minutes. Thereafter the bottle was held in a low temperature bath at 78 C. and varying amounts of triisobutylaluminum solution in toluene (1 molar solu- TABLE 9 Alternating copolymer MEK insoluble, diethyl ether soluble fraction Catalysts MEK Microstructure of butadiene soluble unit (percent) Experiment Ala-Bu); TiCh fraction Yield No. (mmol) (mmol Carbonyl compound Mrnol (g. (55.) Trans- Cis- 1,2-

1.0 0.1 Phosgene 0.1 0.07 1.0 0.1 do 0.2 0.10 1.0 0.1 Acetyl chloride 0.25 0.18 l. 0.1 Titanium oxydiacetylacetonate 1 0.05 0.13 1.0 0.1 Zinc carbonate 0.05 0.05 1.0 0. 1 Sodium carbonate 1 0. 05 0. 08 1.0 0.1 Dimethyl carbonate 0.1 0.22

Example 13 tion) and a mixture of 2 milliliters liquid propylene, 2

The usual, dry, air-free technique was employed and 7.5 milliliters toluene, 0.2 milliliter titanium tetrachloride and 0.5 millimole carbonyl group containing compound were put successively in a 25 milliliters glass bottle at milliliters liquid butadiene and 2 milliliters toluene were put successively into the bottle also employing the usual, dry, air-free technique. Thereafter the bottle was sealed and allowed to copolymerize for 16 hours at 0 C. or ---55 C. The results are summarized in Table 11.

TABLE 11 Alternating copolymer MEK insoluble, diethyl ether soluble fraction Micro structure of Catalysts Polymer- MEK butad iene unit ization soluble (percent) Experiment Al(l-Bu)a T1014 temperatraction Yield No. (mmol) (mmol) Carbonyl compound Mmol ture G.) (g.) (g.) Trans- Cis- 1,2

0.5 0.1 Acetophenone 0.1 55 0.02 0.27 88 8 4 0.5 0.1 ....do 0.1 0 0.16 0.29 70 23 7 0.5 0.1 Isobutyl aldehyda- 0.1 -55 0.01 0.29 76 4 0.5 0 1 d0 0.1 0 0.14 0.20 62 28 10 1.0 0. i 0.25 55 0. 01 0.13 81 16 3 1. 0 0. 0. 25 0 0. 06 1. 14 69 27 4 25 C. Then the bottle was left alone at 25 C. for 10 Example 15 minutes. Thereafter the bottle was held in a low temperature bath at 78 C. and 2.0 milliliters triisobutylaluminum solution in toluene (1 molar solution) and a mixture of 2 milliliters liquid propylene, 2 milliliters liquid butadiene and 2 milliliters toluene were put successively into the bottle also employing the usual, dry, air-free technique. Thereafter the bottle was sealed and allowed to copolymerize at 30 C. for 16 hours. The results are summarized in Table 10.

The usual, dry, air-free technique was employed and varying amounts of carbonyl group containing compound,

6.5 milliliters toluene and varying amounts of titanium tetrachloride were put successively in a 25 milliliters glass bottle at 25 C. Then the bottle was left alone at 25 C. for 10 minutes. Thereafter the bottle was held in a low temperature bath at -78 C. and 2.0 milliliters triisobutylaluminum solution in toluene (1 molar solution) TABLE 10 Alternating copolymer MEK insoluble, diethyl ether soluble action Catalysts MEK Microstructure of butadiene soluble unit (percent) Experiment Al(l-Bu) 'IiCl fraction Yield No. (mmol) (mmol) Carbonyl compound mol (g.) (g.) Trans- 015- 1,2-

2. 0 0. 2 Trimethyl acetic acid 0. 5 0. 42 0.56 2. 0 0. 2 Crotonic acid 0. 5 0.20 0.35 68 28 4. 2. 0 0. 2 Trichloro acetic acid. 0. 5 0. 03 0. l8 2. 0 0. 2 Isobutyric acid anhydrid 0. 5 0. 14 1.29 29 6 2. 0 0. 2 Crotonic acid anhydride 0. 5 0. 0i 0. 57 72 23 5 2. 0 0. 2 Benzoic acid anhydride- 0. 5 O. 10 0. 80 2. 0 0. 2 n-Butyric acid 0. 5 0. 62 0. 80 66 29 7 Example 14 and a mixture of 2 milliliters liquid propylene, 2 milliliters The usual, dry, air-free technique was employed and liquid butadiene and 2 milliliters toluene were put successively into the bottle also employing the usual, dry,

7.0 milliliters toluene, 0.1 millimole titanium tetrachloair-free technique. Thereafter the bottle was sealed and allowed to copolymerize at 30" C. for 16 hours. The results are summarized in Table 12.

TABLE 12 Alternating copolymer MEK insoluble, diethyl ether soluble fraction Microstructure oi Catalysts MEK butadiene unit soluble (percent) Experl- Aid-Bu); TiCh fraction Yield mcnt No. (mmol) (mmol) Carbonyl compound Mmol. (g.) Trans- (315- 1,2-

TlC1:(O 0 CH3) 'l-Pr=Isopropyl; i-Bu=1sobutyl.

Example 16 The usual, dry, air-free technique was employed and 7.0 milliliters toluene, 0.1 millimole titanium tetrachloride and varying amounts of carbonyl group containing compound were put successively in a milliliters glass bottle at 25 C. Then the bottle was left alone at 25 C. for 10 minutes. Thereafter the bottle was held in a low temperature bath at 78 C. and varying amounts of organoaluminum solution in toluene (1 molar solution), 2 milliliters liquid butadiene and 3.1 milliliters liquid 4-methyl pentene-l were put successively into the bottle also employing the usual, dry, air-free technique. Thereafter the bottle was sealed and allowed to copolymerize at C. for 16 hours. The results are summarized in Table 13.

The following results support the conclusion that the copolymer is an alternating copolymer of butadiene and 4-methyl pentene-l.

(1) The composition of the copolymer according to the NMR analysis substantially agrees with the calculated value for the 1:1 copolymer of butadiene and 4-methyl pentene-l.

(2) The copolymerization reaction gives 1:1 copolymer over a wide range of initial monomer composition.

(3) The copolymerization reaction gives 1:1 copolymer independently of polymerization time.

ing copolymer of butadiene and 4-methyl-pentene-l prepared by the process of Exp. No. 4. FIG. 4 shows the nuclear magnetic resonance spectrum of the copolymer.

Example 17 The usual, dry, air-free technique was employed and 7.0 milliliters toluene, 0.1 millimole titaniumtetrahalide and varying amounts of carbonyl group containing compound were put successively in a 25 milliliters glass bottle at 25 C. Then the bottle was left alone at 25 C. for 10 minutes. Thereafter the bottle was held in a low temperature bath at 78 C. and varying amounts of organoaluminum solution in toluene (1 molar solution), 2 milliliters liquid butadiene and 2.8 milliliters liquid pentene-l were put successively into the bottle also employing the usual, dry, air-free technique. Thereafter the bottle was sealed and allowed to copolymerize at -30" C. for 16 hours. The results are summarized in Table 14.

The following results support the conclusion that the copolymer is an alternating copolymer of butadiene and pentene-l.

(1) The composition of the copolymer according to the NMR analysis substantially agrees with the calculated value for the 1:1 copolymer of butadiene and pentene-l.

(2) The copolymerization reaction gives 1:1 copolymer over a wide range of initial monomer composition.

TABLE 13 Alternatin co 1 er Catalysts & Organo t ii l sou e e, e Experiment aluminum T1014 fraction ether soluble No. compound Mmol (mmol) Carbonyl compound 01 (g.) fraction (g.)

1 AlEt; 0.5 0.1 Isobutyl aldehyde .10 0.02 0.03 2 AlEta 1. 0 0.1 Propionic acid anhydride- 0.25 0.05 0.26 3 .A1(1-Bu)a 1.0 0.1 do .2 0.03 0.87 Ala-Bu); 0.5 0.1 Acetophenone 10 0.06 1.05 Ala-Bu); 0.5 0.1 Acetone 0.05 0. 31 Al(i-Bu)s 1.0 0.1 Acetic acid 0.11 0.32 7-- Ala-Bu); 0. 5 0. 1 0. 02 Reierence AlEt; 0.5 0.1 0

17 (3) The copolymerization reaction gives 1:1 mer independently of polymerization time.

copoly- 18 FIG. 7 shows the infra-red spectrum of the methyl ethyl ketone insoluble and diethyl ether soluble alterating TABLE 14 Catalysts Alternating copolymer MEK MEK insoluble, Organosoluble diethyl ether Experiment aluminum Titanium traction soluble No. compound Mmol tetrahalide Mmol Carbonyl compound Mmol (g.) fraction (g.)

1-- AlEta 0.5 T1014 0. 1 Acetophenone.-- 0.10 0.03 0.06 2 A1(i-Bu)a 0.5 T1014 0.1 0.10 0.06 1.02 3 A1(i-Bu) 0.5 T1014 0.1 0.10 0.03 0.43 4---- Al(i-Bu)a 0.5 TiBn 0.1 0.10 0.01 0.13 5 Ala-Bu); 1.0 T1014 0.1 0.25 0.08 0.49

6 Aid-Bu): 1.0 T1014 0.1 (I) 0.02 0.08 0.11

TICMOi JCHa) 7 Ala-Bu); 1 Ti014 0 1 Sameas above 0.10 0.17 0. 84 Al(1-Bu) 1 0 T1014 0 1 Propionlc acid anhyd 0.25 0.01 0.17 Al)i-Bu)a 1 0 T1014 0 1 Isobutyric anhydride. 0.25 0.02 0.19 AMI-Bu): 1 0 T1014 0 1 Acetone 0.10 0.02 0. 76 11 Al(i-Bu); 0 T1014 0.1 0,03 Reference AlEta 0 5 T1014 0.1 0.02

FIG. 5 shows the infra-red spectrum of the methyl ethyl ketone insoluble and diethyl ether soluble alternating copolymer of butadiene and pentene-l prepared by the process of Exp. No. 5. FIG. 6 shows the nuclear magnetic resonance spectrum of the copolymer.

Example 18 The usual, dry, air-free technique was employed and 7.0 milliliters toluene, 0.1 millimole titanium tetrahalide and varying amounts of carbonyl group containing compound were put succesively in a milliliters glass bottle at 25 C. Then the bottle was left alone at 25 C. for 10 minutes. Thereafter the bottle was held in a low temperature bath at 78 C. and varying amounts or organoaluminum compound in toluene (1 molar solution), 2 milliliters liquid butadiene and 2 milliliters liquid butene-l were put successively into the bottle also employing the usual, dry air-free technique. Thereafter the bottle was sealed and allowed to copolymerize at C. for 16 hours. The results are summarized in Table 15.

The following results support the conclusion that the copolymer is an alternating copolymer of butadiene and butene-l.

1) The composition of the copolymer according to the NMR analysis substantially agrees with the calculated value for the 1:1 copolymer of butadiene and butene-l.

(2) The copolymerization reaction gives 1:1 copolymer over a wide range of initial monomer composition.

(3) The copolymerization reaction gives 1:1 copolymer independently of polymerization time.

copolymer of butadiene and butene-l prepared by the process of Exp. No. 4. FIG. 8 shows the nuclear magnetic resonance spectrum of the copolymer.

Example 19 The usual, dry, air-free technique was employed and 5.0 milliliters toluene, 0.1 millimole titanium tetrahalide and varying amounts of carbonyl group containing compound were put successively in a 25 milliliters glass bottle at 25 C. Then the bottle was left alone at 25 C. for 10 minutes. Thereafter the bottle was held in a low temperature bath at 78 C. and varying amounts of organoaluminum solution in toluene (1 molar solution), 3 milliliters styrene and 2 milliliters liquid butadiene were put successively into the bottle also employing the usual, dry, air-free technique. Thereafter the bottle was sealed and allowed to copolymerize at 30 C. for 21 hours. The results are summarized in Table 16.

The following results support the conclusion that the copolymer is an alternating copolymer of butadiene and styrene.

(1) The composition of the copolymer according to the NMR analysis substantially agrees with the calculated value for the 1:1 copolymer of butadiene and styrene.

(2) The copolymerization reaction gives 1:1 copolymer over a wide range of initial monomer composition.

TABLE 1 Catalysts Alternating copolymer MEK MEK insoluble, Organosoluble dlethyl ether Experiment aluminum Titanium fraction soluble No. compound Mmol tetrahalide Mmol Carbonyl compound Mmol (g) 1ractlon(g-.)

AlEta 0.5 T101 0.1 Acetophenone 0.10 0.06 0.15 2-. Ala-Bu); 0.6 T1014 0.1 Isobutyl aldehyde 0.10 0.06 0.26 3 Al(1-Bu)a 1.0 T1014 0.1 Isoamyl acetate. 0.25 0.04 0.14 4.. A1(i-Bll)a 0.5 Ti014 0.1 Benzophenone 0.10 0.04 0.70 5.- Al(i-Bu)3 1.0 T1Br4 0.1 Acetic acid.... 0.25 0.08 0.11 6-. Al(1-Bu):4 1.0 TiBr4 0.1 Acetone 0.25 0.03 0.05 7-- Ala-Bu); 0.5 T1Br4 0.1 Acetophenone 0.10 0.05 1.26 8 Aid-Bu); 0.5 T1014 0.1 0.03 Referenee AlEt; 0.5 T101 0.1 0

19 (3) The copolymerization reaction gives 1:1 copolymer independently of polymerization time.

20 erize at -30 C. for 15 hours. The yield of the alternating copolymer of butadiene and propylene was 0.13 g.

TABLE 16 Catalysts Organo- Alternating Experiment aluminum Titanium copolymer No. compound Mmol tetrahalide Mmol Carbonyl compound Mmol 1 Aid-B11); 1.0 TiGl 0.03 0.5 T101 .10 0.05 0.5 T1014 0 .10 0.05 1.0 TiClt 0. 0.25 0.25 0.5 T1131; 0.1 0.10 0.07 0.5 TiBu 0.1 Tcrephthalaldehyde 0.10 0.11 0.5 TiBrt 0.1 Propionlcacldanl1ydride 0.10 0.04

8 Ala-Bu): 1.0 T1014 0 1 I? 0.10 0.38

TiC1 (OCCHa) Relercnce .AlEti 0.5 T1014 0.1 0

Et=Ethyl; i-Bu=Isobutyl.

FIG. 9 shows the infra-red spectrum of the alternat- 20 Example 22 ing copolymer of butadiene and styrene prepared by the process of Exp. N0. 8. FIG. 10 shows the nuclear magnetic resonance spectrum of the copolymer.

Example The usual, dry, air-free technique was employed and 4.0 milliliters toluene, 0.2 millimole titanium tetrachloride and 0.2 millimole carbonyl containing compound were put successively in a milliliters glass bottle at 25 C. Then the bottle was left alone at 25 C. for 10 minutes. Thereafter the bottle was held in a low temperature bath at 78 C. and varying amounts of triisobutylaluminum solution in toluene (1 molar solution) and 6 milliliters liquid B-B fraction were put successively into the bottle also employing the usual, dry, air-free technique. Thereafter the bottle was sealed and allowed to copolymerize at C. for 24 hours. Alternating copolymer of butadiene and butene-l was obtained. The results are summarized in Table 17. The mole fraction of B-B fraction used was as follows:

Mole percent The usual, dry, air-free technique was employed and 1.0 millimole butadiene, 0.25 millimole propionic acid anhydride and 0.1 millimole titanium tetrachloride were putsuccessively into a 25 milliliters glass bottle at 25 C. Then the bottle was held in a low temperature bath at 78 C. and 10 milliliters triisobutylaluminum solution in toluene (1 mole solution) and a mixture of 3 milliliters liquid propylene, 2 milliliters liquid butadiene and 2 milliliters toluene were put successively into the bottle also employing the usual, dry, air-free technique. Thereafter the bottle was sealed and allowed to copolymerize at -30 C. for 15 hours. The yield of the alternating copolymer of butadiene and propylene was 0.65 g. and the microstructure of butadiene unit of the copolymer was as follows:

trans: 70% cis: 22% 1,2: 8%

Example 23 The usual, dry, air-free technique was employed and a mixture of 2 milliliters liquid propylene, 2 milliliters liquid butadiene and 2 milliliters toluene, 0.18 millimole j fggzf i 8'8; titanium tetrachloride, 0.6 milliliter of triisobutylalumi- Methyl acetylene num solution in toluene (1 molar solution) and 0.12 milli- Isobutane mole acetophenone were put successively at intervals of mButane 10 minutes into a 25 milliliters glass bottle at 78 C. lsobutylel'l'e "T: 26'22 Thereafter the bottle was sealed and allowed to copolym- Buterwl 14'18 erize at -40 C. for 4.5 hours. The yield of the alternat- Trans butene z ing copolymer of butadiene and propylene was 0.60 g. cis butene z 412 and the microstructure of butadiene unit of the copoly- 1,3-butadiene 44.02 was as 1,2-butadiene 0.52 trans: 92% Ethyl acetylene 0.16 cis: 6% Vinyl acetylene 0.64 1.2: 2%

TABLE 17 Alternating copolymer Catalysts MEK MEK insolusoluble ble, dlethyl Experiment AMI-Bu); T1014 Carbonyl fraction ether soluble No. (mmol) (mmol) compound Mmol (g. traction (g.)

1 1.0 0.2 Acetophen0ne... 0.2 0.14 0.02 2 2.0 0.2 0 0.2 0.10 0.56

T101, 0(JJCH:

Example 21 Example 24 The usual, dry, air-free technique was employed and 7.0 milliliters toluene, 1.0 milliliter triisobutylaluminum solution in toluene (1 molar solution), 0.25 millimole propionic acid anhydride, 0.1 millimole titanium tetrachloride and a mixture of 2 milliliters liquid propylene, 2 milliliters liquid butadiene and 2 milliliters toluene were put successively into a 25 milliliters glass bottle at -7 8 The usual, dry, air-free technique was employed and a mixture of 2 milliliters liquid propylene, 2-milliliters liquid butadiene and 2 milliliters toluene, 0.18 millimole titanium tetrachloride, 0.12 millimole acetophenone and 0.6 milliliter triisobutylaluminum solution in toluene (1 molar solution) were put successively at intervals of 10 minutes into a 25 milliliters glass bottle at -78 C C. Then the bottle was sealed and allowed to copolym- 7 Thereafter the bottle was sealed and allowed to cotrans: 91% csi: 7% 1.2: 2%

Example 25 The usual, dry, air-free technique was employed and a mixture of 2 milliliters liquid propylene, 2 milliliters liquid butadiene and 2 milliliters toluene, 0.6 milliliter triisobutylaluminum solution in toluene (1 molar solution), 0.12 millimole acetophenone and 0.18 millimole 22 25 milliliters glass bottle at 25 C. Then the bottle was left alone at 25 C. for 10 minutes. Thereafter the bottle washeld in a low temperature bath at -78 C. and 2.0 milliliters triisobutylaluminum solution in toluene (1 molar solution) and a mixture of 2 milliliters liquid propylene, 2 milliliters liquid butadiene and 2 milliliters toluene were put successively into the bottle also employing the usual, dry, air-free technique. Thereafter the bottle was sealed and allowed to copolymerize at --30 C. for 16 hours. The results are summarized in Table 18. As can be seen in Table 18, the yield of the high molecular weight alternating copolymer of butadiene and propylene increased by adding metal oxide or metalloid oxide to the three components catalyst system of organoaluminum titanium tetrachloride were put successively at intervals 15 compound, titanium tetrahalide and carbonyl compound.

TABLE 18 Alternating copolymer Catalysts MEK MEK insolusoluble ble, diethyl Experiment Al(l-Bu)a TiCli Metal oxide or fraction ether soluble No. (mmol) (mmol) Carbonyl compound Mmol metalloid oxide Gram (g.) fraction (g.)

2. 0. 2 Monoehloroacetic acid. 0. Titanium dioxode 0. 05 0.23 0. 82 2. 0 0. 5 0. 17 0. 29 2. 0 0. 5 0.17 0. 48 2. 0 0. 5 0.09 0.14 2. 0 0. 5 Vanadium pentox e 0. 23 0.56 2.0 0.5 Silica 0.05 0.22 0.15 2. 0 0. 5 0.08 0 04 2. 0 0. 5 1. 48 0. 67 2. 0 0. 5 0.23 0. 47 2. 0 0. 5 0. 24 0. 22 2. 0 0. 6 0. 24 0. 13 2. 0 0. 5 0. 12 0.93 2. 0 0. 5 0. l3 0. 83

*Butadlenc mlcrostructure: Trans=73%; Cis=12%; 1.2=5%.

of minutes into a 25 milliliters glass bottle at -78 C. Thereafter the bottle was sealed and allowed to copolymerize at C. for 4.5 hours. The yield of the alternating copolymer of butadiene and propylene was 1.01 g.

Example 26 The usual, dry, air-free technique was employed and 0.05 g. metal oxide or metalloid oxide, 6.5 milliliters toluene, 0.2 milliliter titanium tetrachloride solution in toluene (1 molar solution) and 0.5 millimole carbonyl group containing compound were put successively in a EXAMPLE 28 The usual, dry, air-free technique was employed and 6.0 milliliters toluene, 0.5 millimole carbonyl group containing compound, 0.2 milliliter titanium tetrachloride solution in toluene (1 molar solution) and 0.2 millimole halogen or halogen compound were put successively in a 25 milliliters glass bottle at 25 C. Then the bottle was left alone at 25 C. for 10 minutes. Thereafter the bottle was held in a low temperature bath at 78 C. and 2.0 milliliters triisobutylaluminum solution in toluene (1 molar solution) and a mixture of 2 milliliters liquid propylene, 2 milliliters liquid butadiene and 2 milliliters toluene were put successively into the bottle also employing the usual, dry, air-free technique. Thereafter the bottle was sealed and allowed to copolymerize at 30 C. for 16 hours. The results are summarized in Table 19.

As can be seen in Table 19, the yield of the high molecular weight alternating copolymer of butadiene and propylene was increased by adding halogen or halogen compound to the three components catalyst system of organoaluminum compound, titanium tetrachloride and carbonyl compound.

TABLE 19 Catalysts Alternating copolymer MEK MEK insoluble, soluble diethyl ether Experiment Al(l-Bu)a T1014 Carbonyl Halogen or halogen comfraction soluble frac- No. (mmol) (mmol) compound Mmol pound Mmol (g.) tion (g.)

1 2.0 0.2 Benzophenone-.... 0.5 Stannic chloride 0.2 0.16 0.79 Reference 1..- 2.0 0.2 0 0 5 0.23 0.57 2 2.0 0.2 Benzoy1peroxlde 0.12 0.25 2.0 0.2 0 0.11 0.20 2.0 0.2 Ethyl acetate 0.5 Etlilglaluminum dlehlo- 0.19 0.54

r e. Reierence3. 2. 0 0. 2 0. 5 0.09 0. 14 4 2.0 0.2 0.5 Aluminum bromide. 0. 09 0.13 Reference 4 2. 0 0. 2 0. 5 0.08 0. 04 5 2. 0 0. 2 0. 5 A1C1z'O(CzH5)2 0. 2 0.18 0. 40 Reference 5 2.0 0.2 n 0.24 0.13 .0 0.2 Benzophenone 0.5 Iodine. 0.2 0.15 0.67

Butadlene mierostrueture: Trans=67%; Cls=25%; 1.2=8%.

EXAMPLE 29 The usual, dry, air-free technique was employed and 6.0 milliliters toluene, 0.5 millimole isobutyl aldehyde,

ratio of triisobutylaluminum to titanium tetrachloride is 1.5 (Al/Ti=1.5) no alternating copolymer can be obtained TABLE 20 Alternatin'co 01 met Catalysts MEK MEK in- Organo- Diluent soluble soluble, diethyl Experiment. aluminum TiCli toluene fraction ether soluble No. compound Mmol (mmol) Halogen or halogen compound Minol. (1111.) (g.) fraction (g.)

1 A1(i-Bu) 2.5 1.0 5 o 0.0:) Al(i-Bu) 2.5 1. Chromium (VI) 0xychlorido 1.2 0. 40 1.00 Alti-Bu); 2. 5 1. 0 Vanadium (V) oxychloride 1.0 4 0.89 0.58 Aid-Bu); 2.5 1. 0 tert-Butyl chloride 2. 5 5 0.10 0.14 Alti-Bu); 2.5 1.0 Bromine-. 0.8 5 0.08 0.34 Alti-Bu); 1.5 1.0 5 0 0 AlEts 2. 5 1. 0 5 0 0 Reference 3-..- AlEt; 1. 5 1. 0 5 0 o 0.2 milliliter titanium tetrachloride solution in toluene (1 molar solution) and 0.2 millimole boron trifiuoride diethyl ether complex were put successively in a 25 milliliters glass bottle at 25 C. Then the bottle was left alone at 100 C. for minutes. Thereafter the bottle was held in a low temperature bath at 78 C. and 2.0 milliliters triisobutylaluminum solution in toluene (1 molar solution) and a mixture of 2 milliliters liquid butadiene and 2 milliliters toluene were put successively into the bottle also employing the conventional, dry, air-free technique. Thereafter the bottle was sealed and allowed to copolymerize at 30 C. for 16 hours. The yield of methyl ethyl ketone soluble alternating copolymer of butadiene and propylene was 0.18 g. and that of methyl ethyl ketone insoluble and diethyl ether soluble fraction, i.e. alternating copolymer of butadiene and propylene was 0.74 g. When the three components catalyst system consisting of triisobutylaluminum, titanium tetrachloride and isobutylaldehyde was used and the other copolymerization conditions were the same as those in this example, the yield of the high molecular weight alternating copolymer was 0.47 g.

EXAMPLE 30 The usual, dry, air-free technique was employed and varying amounts of toluene, 1.0 milliliter titanium tetrachloride solution in toluene (1 molar solution) and varying amounts of halogen or halogen compound were put successively in a 25 milliliters glass bottle at 25 C. Then the bottle was left alone at 25 C. for 10 minutes. Thereafter the bottle was held in a low temperature bath at 78 C. and varying amounts of organoaluminum com- Example 31 0 the bottle also employing the usual, dry, air-free technique. Thereafter the bottle was sealed and allowed to copolymerize at 30 C. for 16 hours. The yield of alternating copolymer of butadiene and styrene was 0.53 g.

Example 32 The usual, dry, air-free technique was employed and 0.5 millimole halogen compound, 6.5 milliliters toluene and 0.2 milliliter titanium tetrachloride solution in toluene (1 molar solution) were put successively in a milliliter glass bottle at 25 C. Then the bottle was left alone at 25 C. for 10 minutes. Thereafter the bottle was held in a low temperature bath at 78 C. and 2.0 milliliters triisobutylaluminum solution in toluene (1 molar solution) and a mixture of 2 milliliters liquid propylene, milliliters liquid butadiene and 2 milliliters liquid toluene were put successvely into the bottle also employing the usual, dry, air-free technique. Thereafter the bottle was sealed and allowed to copolymerize at C. for 16 hours. The results are summarized in Table 21.

pound in toluene (1 molar solution) and a mixture of 5 2 milliliters liquid propylene, 2 milliliters liquid butadiene and 2 milliliters toluene were put successively into the bottle also employing the usual, dry, air-free technique. Thereafter the bottle was sealed and allowed to copolymerize at 30 C. for 16 hours. The results are summarized in Table 20. As can be seen in Table 20, by adding halogen or halogen compound to the two components catalyst system consisting of organoaluminum compound and titanium tetrahalide, the yield of the alternating copolymer increased. Ref. 1 also shows that when the mol The usual, dry, air-free technique was employed and 0.5 millimole halogen compound, 6.5 milliliters toluene and 0.2 milliliter titanium tetrachloride solution in toluene (1 molar solution) were put successively in a 25 milliliter glass bottle at 25 C. Then the bottle was left alone at 25 C. for 10 minutes. Thereafter the bottle was held in a low temperature bath at 78 C. and 2.0 milliliters triisobutylaluminum solution in toluene (1 molar solution) and a mixture of 2 milliliters liquid propylene, 2 milliliters liquid butadiene and 2 milliliters toluene were put successively into the bottle also employing the usual, dry, air-free technique. Thereafter the bottle was sealed and allowed to copolymerize at 30" C.

2. A process as claimed in claim 1, wherein the catalyst system contains a material selected from the group consisting of a metal oxide, a metalloid oxide, a halogen and a halogen compound as a fourth component.

for 39 hours. The results are summarized in Table 22. 5 3. A process as claimed in claim 1, wherein the molar TABLE 22 Catalysts Alternating copolymer MEK MEK insoluble A1 (Him) a T1014 Halogen mmol) soluble diethyl ether Mmol fraction soluble fraetgon 2 0.2 BlCh-CEti 5 0.10 0.52 2 0.2 SnCh-OEtz 0 5 0.02 0.15 2 0.2 BCla-OEta 0 5 0.02 0.10 2 0.2 0 0.05

*Et=Ethyl.

Example 34 ratio of the organoaluminum compound to the titanium The usual, dry, air-free technique was employed and 0.5 millimole bismuth (III) chloride diethyl ether complex, 6.5 milliliters toluene and 0.2 milliliter titanium tetrachloride solution in toluene (1 molar solution) were put successively in a 25 milliliters glass bottle at 25 C. Then the bottle was left alone at 25 C. for minutes. Thereafter the bottle was held in a low temperature bath at 78 C. and 2.0 milliliters triethylaluminum solution in toluene and a mixture of 2 milliliters liquid propylene, 2 milliliters liquid butadiene and 2 milliliters toluene were put successively into the bottle also employing the usual, dry, air-free technique. Thereafter the bottle was sealed and allowed to copolymerize at 30 C. for 16 hours. The yield of methyl ethyl ketone soluble alternating copolymer of butadiene and propylene was 0.05 g. and methyl ethyl ketone insoluble and diethyl ether soluble alternating copolymer of butadiene and propylene was 0.11 g. By using two components catalyst system of triethylaluminum and titanium tetrachloride, no alternating copolymer of butadiene and propylene was obtained.

What we claim is:

1. A process for preparing a 1:1 copolymer of butadiene and an alpha-olefin having alternating butadiene and alpha-olefin units, said alpha-olefin having the general formula of CH =CHR' wherein R represents a phenyl radical or a C to C normal or branched chain alkyl radical, which comprises contacting butadiene and the alpha-olefin in liquid phase at a temperature of from 100 C. to 50 C. with a catalyst system comprising a first component of an organoaluminum compound having the general formula of AlR wherein R represents a hydrocarbon radical selected from the group consisting of an alkyl radical, an aryl radical and a cycloalkyl radical, a second component of titanium tetrahalide having the general formula TiX wherein X' is selected from the group consisting of chlorine, bromine and iodine, and a third component of a carbonyl group-containing compound, wherein the molar ratio of said organoaluminum compound to said titanium tetrahalide is from greater than 1.5 to 20 and the molar ratio of butadiene to said alpha-olefin in the initial monomer composition is within a range of from 20:80 to 80:20.

tetrahalide is approximately 1.5-10.

4. A process as claimed in claim 1, wherein said halogen compound is selected from the group consisting of a halogen compound having Lewis acid property, a Lewis acid-base complex of a halogen compound having Lewis acid property, an organoaluminum compound having an Al-X linkage, an organotransition-metal compound having a transition metal-X linkage and an alkane compound having a C-X linkage, wherein X represents halogen.

5. A process as claimed in claim 1, wherein the polymerization reaction is carried out in the presence of a hydrocarbon diluent.

6. A process as claimed in claim 1 wherein the molar ratio of butadiene to the alpha-olefin in the initial monomer composition is substantially 50:50.

7. A process as claimed in claim 1, wherein said a-olefin is styrene.

8. A process as claimed in claim 1, wherein said a-olefin is selected from the group consisting of propylene, butene-l, pentene-l and hexene-l.

9. A process as claimed in claim 1, wherein said u-olefin is 4-methyl pentene-l.

References Cited UNITED STATES PATENTS 3,317,496 5/1967 Natta et al. 260882 3,470,144 9/1969 Minekawa et al 260 .3 3,506,632 4/1970 Henderson 26085.3 3,210,332 10/1965 Lyons et al. 26093.7 3,462,406 8/1969 Natta et al. 260--94.3 3,466,268 9/1969 Burton et al 26085.3 3,652,518 3/1972 Kawasaki et al. 26085.3 R 3,652,519 3/1972 Kawasaki et al. 26085.3 R 3,700,638 10/ 1972 Kawasaki et al. 260--85.3 R 3,714,133 1/ 1973 Kawasaki et a1 26084.1

JOSEPH L. SCHOFER, Primary Examiner A. HOLLER, Assistant Examiner US. Cl. X.R.

26032.8 A, 33.2 R, 79.5 B, 79.5 C, 83.7, 85.3 R, 85.3 C, 88.2 E 

